CN108264747A - It shows good heat-resisting and insulation performance resin combination and uses its product - Google Patents

It shows good heat-resisting and insulation performance resin combination and uses its product Download PDF

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Publication number
CN108264747A
CN108264747A CN201711143292.4A CN201711143292A CN108264747A CN 108264747 A CN108264747 A CN 108264747A CN 201711143292 A CN201711143292 A CN 201711143292A CN 108264747 A CN108264747 A CN 108264747A
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resisting
resin combination
insulation performance
good heat
vinyl
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丁赫镇
金明焕
申承湜
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Lotte Advanced Materials Co Ltd
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Lotte Advanced Materials Co Ltd
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    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
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    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
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    • C08F279/06—Vinyl aromatic monomers and methacrylates as the only monomers
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    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
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    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
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Abstract

The present invention relates to show good heat-resisting and insulation performance resin combination and use its product, good heat-resisting and insulation performance resin combination is shown more particularly to according to illustrative embodiments, it includes (A) polycarbonate resins, (B) vinyl-based copolymer, (C) fire retardant based on phosphorus that fluorinated polyolefin and (D) chemical formula 1 represent, wherein, in chemical formula 1, each R6、R7、R9And R10It is independently C6 to C20 aryl groups or alkyl-substituted aryl group, R8It is biphenyl phenolic group, and the integer that n is 1 to 5.[chemical formula 1]

Description

It shows good heat-resisting and insulation performance resin combination and uses its product
The citation of related application
This application claims the South Korea patent application 10- for enjoying submission on December 30th, 2016 Korean Intellectual Property Office The priority and equity of No. 2016-0184153, entire contents are incorporated herein by being cited.
Technical field
This disclosure relates to the resin combination and the product using its manufacture that show excellent heat resistance and insulating properties.
Background technology
Polycarbonate resin is the engineering plastics for having excellent mechanical strength, high-fire resistance, the transparency etc., therefore can be with It is for various fields, such as the resin of business automation equipment, electrical/electronic components, construction material.
Specifically, excellent insulation performance and heat resistance are needed for accommodating the polycarbonate resin of electrical/electronic components And high flame retardant and impact resistance.
In general, in order to improve the anti-flammability of polycarbonate resin, the fire retardant for example based on bisphenol-A phosphate can be used Deng.However, the anti-flammability can be improved, but heat resistance and insulating properties may be deteriorated drastically.
Therefore, it is necessary to develop to have the new of improved insulation performance and heat resistance and excellent anti-flammability and impact resistance Type resin combination.
Invention content
One illustrative embodiments provide with improved insulation performance and heat resistance and improved anti-flammability and The resin combination of impact resistance.
Another embodiment provides the products manufactured by the resin combination.
(A) is included according to the resin combination for showing excellent heat resistance and insulating properties of an illustrative embodiments Polycarbonate resin, (B) vinyl-based copolymer, (C) fluorinated polyolefin and (D) chemical formula 1 represent based on the fire-retardant of phosphorus Agent.
[chemical formula 1]
Wherein, in chemical formula 1,
R6、R7、R9And R10It is C6 each independently to C20 aryl groups or alkyl-substituted aryl group,
R8It is xenol, and
N is the integer in the range of 1 to 5.
Can be that biphenyl -4,4'- diyl tetraphenyls are bis- (phosphate) by the fire retardant (D) based on phosphorus that chemical formula 1 represents.
Good heat-resisting and insulation performance resin combination is shown to be based on showing good heat-resisting and insulation performance The total amount of resin combination can include the polycarbonate resin (A) of about 65wt% to about 94wt%, about 1wt% is to about The vinyl-based copolymer (B) of 20wt%, the fluorinated polyolefin (C) of about 0.01wt% to about 2wt% and about 1.5wt% are to about The fire retardant (D) based on phosphorus that 15wt% is represented by chemical formula 1.
Polycarbonate resin, which can include (A-1) first polycarbonate resin and (A-2), has different weight average molecular weight The second polycarbonate resin.
The weight average molecular weight of first polycarbonate resin (A-1) can be in about 25,000g/mol to about 32,000g/mol models In enclosing, and the weight average molecular weight of the second polycarbonate resin (A-2) can be in about 20,000g/mol to about 25,000g/mol models In enclosing.
Polycarbonate resin based on 100wt%, polycarbonate resin can include the of about 25wt% to about 65wt% The second polycarbonate resin (A-2) of one polycarbonate resin (A-1) and about 35wt% to about 75wt%.
Vinyl-based copolymer can include the vinyl-based graft copolymer of (B-1) modified rubber, and (B-2) uses (methyl) The vinyl-based graft copolymer of modified rubber of acrylate compounds grafting and (B-3) aromatic vinyl compound-ethylene At least one of base cyanogen compound copolymer.
The vinyl-based graft copolymer of modified rubber can be acrylonitrile-butadiene-phenylethene grafted copolymer (g- ABS)。
The vinyl-based graft copolymer for the modified rubber being grafted with (methyl) acrylate compounds can be methyl-prop E pioic acid methyl ester-butadiene-styrene copolymer (MBS).
Aromatic vinyl compound-vinyl cyanide compound copolymer can be styrene-acrylonitrile copolymer (SAN).
According to an illustrative embodiments, provide using the resin combination for showing good heat-resisting and insulation performance The product of object.
Product can have the relative discharge tracking index (CTI) according to ASTM D3638-12 about 0 to about 2 measured.
Can have according to the resin combination of illustrative embodiments and using product of its manufacture improve it is exhausted Edge performance and heat resistance and improved anti-flammability and impact resistance.
Specific embodiment
Hereinafter, it will be described in embodiment of the present disclosure.However, these embodiments are exemplary, the disclosure It is without being limited thereto, and the disclosure is limited by the scope of the claims.
As used herein, when no in addition offer definition, " substituted " refers to by C1 to C30 alkyl groups；C1 to C10 AIkylsilyl groups group；C3 is to C30 groups of naphthene base；C6 is to C30 aryl groups；C2 is to C30 heteroaryl groups；C1 to C10 Alkoxy base；Fluorin radical；C1 is to C10 trifluoroalkyl groups such as trifluoromethyl group；Or cyano group is replaced in compound At least one hydrogen.
As used herein, when no in addition offer definition, term " miscellaneous " can refer to include 1 in compound or substituent group To 3 hetero atoms selected from N, O, S and P and remaining carbon.
As used herein, when no in addition offer definition, term " alkyl group " can refer to be free of alkylene group Or " the saturated alkyl group " of alkynyl group；Or include " the unsaturated alkane of at least one of alkylene group and alkynyl group Base group ".Term " alkenyl group " can refer to the substitution that wherein at least two carbon atom is combined at least one carbon-to-carbon double bond Base, and term " alkynyl group " refers to the substituent group that wherein at least two carbon atom is combined at least one carbon-carbon triple bond.Alkane Base group can be branch, straight chain or cricoid alkyl group.
Alkyl group can be C1 to C20 alkyl groups, specifically C1 to C6 low-grade alkyl groups, C7 to C10 middle rank alkane Base group or C11 are to C20 higher alkyl groups.
Term " aromatic hydrocarbons " can refer to the compound for including cyclic structure, and wherein all elements all have the p for forming conjugation Track.Its specific example can be aryl group and heteroaryl groups.
Term " aryl group " can refer to monocyclic or polycyclic (that is, ring of shared adjacent carbon atom pair) containing condensed ring Group.
" heteroaryl groups " can refer to the group comprising 1 to 3 hetero atom selected from N, O, S or P and remaining carbon.When When heteroaryl groups are fused rings, each ring can include 1 to 3 hetero atom.
As used herein, when no additional specific definition is provided, (methyl) acrylate refers to acrylate or methyl Acrylate.In addition, (methyl) alkyl acrylate refers to alkyl acrylate or alkyl methacrylate, and (methyl) third Olefin(e) acid ester refers to acrylate or methacrylate.
As used herein, when no in addition offer definition, " copolymerization " can refer to block copolymerization, random copolymerization, grafting Copolymerization or alternating copolymerization, and " copolymer " can refer to block copolymer, random copolymer, graft copolymer or alternating copolymerization Object.
According to illustrative embodiments, show good heat-resisting and insulation performance resin combination and include (A) poly- carbon Acid ester resin, (B) vinyl-based copolymer, the fire retardant based on phosphorus that (C) fluorinated polyolefin and (D) are represented by chemical formula 1.
[chemical formula 1]
Wherein, in chemical formula 1,
Each R6、R7、R9And R10It is independently C6 to C20 aryl groups or alkyl-substituted aryl group, R8It is xenol Base, and the integer that n is 1 to 5.
Hereinafter, each component for the resin combination for showing good heat-resisting and insulation performance will be described in detail.
(A) polycarbonate resin
In an illustrative embodiments, polycarbonate resin is the polyester for having carbonic acid ester bond, is not particularly limited, And can be any makrolon that can be used for resin combination field.
For example, polycarbonate resin can by the diphenol that makes to be represented by chemical formula 2 and phosgene, halate, carbonic ester or A combination thereof is reacted and is prepared.
[chemical formula 2]
In chemical formula 2,
A is selected from singly-bound, substituted or unsubstituted C1 to C30 alkylidene groups, substituted or unsubstituted C2 to C5 Asias alkene Base group, substituted or unsubstituted C2 to C5 alkyliden groups, substituted or unsubstituted C1 to C30 halogeno alkylens group, take Generation or unsubstituted C5 are to C6 cycloalkylene groups, substituted or unsubstituted C5 to C6 Asias cycloalkenyl groups, substitution or unsubstituted C5 it is sub- to C10 rings alkyliden group, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C1 to C20 Alkoxy base, hydracid ester group, carbonate group, CO, S and SO2Linking group, R1And R2It is independently to replace or do not take The C1 in generation is to C30 alkyl groups or substituted or unsubstituted C6 to C30 aryl groups, and n1 and n2 are independently in the range of 0 to 4 Integer.
Two or more diphenol represented by chemical formula 2 can combine the repetitive unit to form polycarbonate resin.
The specific example of diphenol can be quinhydrones, resorcinol, 4,4' dihydroxy diphenyl, 2,2- bis- (4- hydroxy phenyls) Propane (being known as " bisphenol-A "), bis- (4- the hydroxy phenyls) -2- methybutanes of 2,4-, bis- (4- hydroxy phenyls) methane, the bis- (4- of 1,1- Hydroxy phenyl) hexamethylene, bis- (the 3- chloro-4-hydroxyls phenyl) propane of 2,2-, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, 2, Bis- (bis- chloro- 4- hydroxy phenyls of the 3,5-) propane of bis- (3,5- dimethyl -4- hydroxy phenyls) propane of 2-, 2,2-, the bis- (3,5- bis- of 2,2- Bromo- 4- hydroxy phenyls) propane, bis- (4- hydroxy phenyls) sulfoxides, bis- (4- hydroxy phenyls) ketone, bis- (4- hydroxy phenyls) ethers etc.. It is preferable to use bis- (4- hydroxy phenyls) propane of 2,2-, bis- (3- methyl -4- hydroxy phenyls) propane of 2,2-, 2,2- in diphenol Bis- (bis- chloro- 4- hydroxy phenyls of the 3,5-) propane of bis- (3,5- dimethyl -4- hydroxy phenyls) propane, 2,2- or bis- (the 4- hydroxyls of 1,1- Phenyl) hexamethylene.Bis- (4- hydroxy phenyls) propane of 2,2- can more preferably be used.
Polycarbonate resin can be the mixture of copolymer obtained using two or more diphenol different from each other.
In addition, polycarbonate resin can be that Linear polycarbonate resin, branched polycarbonate resin, polyestercarbonate are common Copolymer resin etc..
The specific example of Linear polycarbonate resin can be bisphenol A polycarbonate resin.Branched polycarbonate resin Specific example can be by making multifunctional aromatic compounds such as trimellitic anhydride, trimellitic acid etc. and diphenol and carbonate reaction And the polymer prepared.Polyester carbonate copolymer resin can be by making bifunctional carboxylic acid be made with diphenol and carbonate reaction It is standby, wherein the carbonic ester used is diaryl carbonate such as diphenyl carbonate or ethylene carbonate.
The total amount for showing good heat-resisting and insulation performance resin combination based on the disclosure, can be with about 65wt% is to about 94wt%, for example, the amount of about 70wt% to about 93wt% includes polycarbonate resin.When polycarbonate resin When amount is less than about 65wt%, appearance characteristics, mechanical strength and heat-resistant quality are unfavorable, and when it is greater than about 94wt%, stream Dynamic property may be decreased.
Herein, polycarbonate resin can include (A-1) first polycarbonate resin and (A-2) and have and the first poly- carbon Second polycarbonate resin of the different weight average molecular weight of acid ester resin.
The weight average molecular weight of first polycarbonate resin (A-1) can be in about 25,000g/mol to about 32,000g/mol's In the range of, the weight average molecular weight of the second polycarbonate resin (A-2) can be in about 20,000g/mol to about 25,000g/mol's In the range of.
In addition, the polycarbonate resin based on 100wt%, polycarbonate resin can include about 25wt% to about 65wt%'s The second polycarbonate resin (A-2) of first polycarbonate resin (A-1) and about 35wt% to about 75wt%.
When the weight average molecular weight and amount of the first and second polycarbonate resins are respectively in the range of these, have good Heat-resisting and insulation performance resin combination can have excellent impact resistance.In addition, have by mixing respective heavy First and second makrolon of average molecular weight, polycarbonate resin can have desired mobility.
(B) vinyl-based copolymer
It shows good heat-resisting and insulation performance resin combination according to illustrative embodiments and can wrap Containing vinyl-based copolymer.Vinyl-based copolymer can improve the resin combination for showing good heat-resisting and insulation performance Impact resistance.Vinyl-based graft copolymer, the rubber that this vinyl-based copolymer can include such as modified rubber change At least one of aromatic ethylene based co-polymers and aromatic vinyl compound-vinyl cyanide compound copolymer of property.
In addition, the total amount based on the resin combination for showing good heat-resisting and insulation performance, vinyl-based copolymer Amount can be about 1wt% to about 20wt% or about 3wt% to about 15wt%.When the amount of vinyl-based copolymer is greater than or equal to During about 1wt%, it can be ensured that improved impact resistance, and when it is less than or equal to about 20wt%, it can be ensured that anti-flammability And thermal stability.
This vinyl-based copolymer can be used alone or be used with the mixture of two or more.
Hereinafter, it will be described in the example of vinyl-based copolymer.
(B-1) the vinyl-based graft copolymer of modified rubber
The vinyl-based graft copolymer (B-1) of modified rubber can be and aromatic ethylene base class monomer and aromatic vinyl The monomer grafting of class monomers copolymerizable selected from butadiene rubber, styrene/butadiene rubbers, acrylonitrile/butadiene rubber, different Pentadiene rubber, ethylene/propylene rubber, Ethylene-Propylene-Diene trimer (EPDM) rubber and polysiloxane/poly- (first Base) alkyl acrylate rubbers rubber-like polymer.
For example, the amount of rubber-like polymer can be the total weight of the vinyl-based graft copolymer of modified rubber The about 5wt% of (100wt%) is to about 65wt%, for example, about 10wt% to about 60wt%, particularly from about 20wt% is to about 50wt%.When rubber-like polymer meets the range of the amount, it is according to illustrative embodiments show it is good it is heat-resisting and The resin combination of insulation performance can have improved impact resistance, mechanical performance etc..
The average grain diameter of rubber-like polymer can use its system in the range of about 0.1 μm to about 10 μm to improve The impact resistance of product and surface characteristic.For example, the average grain diameter of rubber-like polymer can be at about 0.15 μm to about 6 μm, for example, about 0.15 μm to about 4 μm, for example, in the range of about 0.25 μm to about 3.5 μm.In the range, resin combination may insure Excellent impact strength.
Aromatic ethylene base class monomer can be with graft copolymerization on rubbery copolymer, and can be such as styrene, C1- Styrene, halogen-substituted styrene or the combination thereof of C10 alkyl groups substitution.For example, aromatic ethylene base class monomer can be with It is o-ethyl styrene, m-ethyl styrene, p -ethyl-styrene, α-methylstyrene etc., but not limited to this, and can be single Solely or with the mixture of two or more use.
The total weight of vinyl-based graft copolymer (B-1) based on modified rubber, the amount of aromatic ethylene base class monomer can About 15wt% is thought to about 94wt%, for example, about 20wt% is to about 80wt%, for example, about 30wt% to about 60wt%.Work as aromatics When vinyl monomer meets the range of the amount, impact resistance, mechanical performance etc. can be improved.
Monomer with aromatic ethylene base class monomers copolymerizable can be such as vinyl cyanide class monomer such as acrylonitrile, methyl-prop Alkene nitrile, ethyl acrylonitrile, phenyl acrylonitrile, α-chloro-acrylonitrile, flumaronitrile etc., and can be used alone or with two or more The mixture of kind uses.
The total weight of vinyl-based graft copolymer (B-1) based on modified rubber, the amount of vinyl cyanide class monomer can be with Be about 1wt% to about 20wt%, for example, about 5wt% to about 15wt%.When including vinyl cyanide class monomer in the range, Excellent impact resistance and heat resistance can be obtained.
The vinyl-based graft copolymer of modified rubber according to illustrative embodiments can pass through emulsion polymerization, suspension It is prepared by the polymerization of polymerization, bulk polymerization or combination thereof.
For example, the vinyl-based graft copolymer of the modified rubber prepared by the above method can be, such as acrylonitrile- Butadiene-styrene (ABS) graft copolymer.
Total amount based on resin combination, the amount of the vinyl-based graft copolymer (B-1) of modified rubber can be about 1wt% to about 6wt%, particularly from about 2wt% are to about 5wt%.Vinyl-based grafting comprising the modified rubber in the range of this is total to The resin combination of polymers shows excellent impact resistance and heat resistance.
(B-2) the vinyl-based graft copolymer for the modified rubber being grafted with (methyl) acrylate compounds
The vinyl-based graft copolymer (B-2) of modified rubber being grafted with (methyl) acrylate compounds can be Core-shell type copolymer, center are rubber-like polymers, and shell is aromatic ethylene base class compound, (methyl) acroleic acid esterification Close object and its copolymer.
Polymerization can be any method well known in the art, gather without any special limitation, such as bulk polymerization, suspension Conjunction, emulsion polymerization etc..
For example, (B-2) copolymer can by will about 40wt% to about 60wt% aromatic ethylene base class compound and (first Base) acrylate compounds mixture in the presence of about 40wt% to the rubber-like polymer of about 60wt% use emulsion polymerization Method is graft-polymerized and prepares.When in the range use rubber-like polymer, aromatic ethylene base class compound and (methyl) third During the mixture of enoic acid ester compounds, excellent impact resistance, heat resistance of resin combination etc. can be obtained.
Herein, rubber-like polymer can form stratum nucleare.Rubber-like polymer can have about 200nm to about 400nm In the range of average grain diameter.When rubber-like polymer has the average grain diameter less than about 200nm, impact resistance may deteriorate, But when rubber-like polymer has the greater than about average grain diameter of 400nm, machinability may deteriorate.
According to the illustrative embodiments of the disclosure, rubber-like polymer can be selected from polybutadiene rubber, acrylic acid Class rubber, ethylene/propylene rubber, styrene/butadiene rubbers, acrylonitrile/butadiene rubber, polyisoprene rubber, ethylene- One kind in propylenediene trimer (EPDM) and polysiloxane/poly- (methyl) alkyl acrylate rubbers composite material Or the mixture of two or more.More specifically, polybutadiene rubber can be used.
On the other hand, the aromatic ethylene base class compound for forming shell can be replaced selected from styrene, C1-C10 alkyl The styrene, styrene of halogen substitution, vinyltoluene, one or more in vinyl naphthalene and combination thereof.Alkyl The specific example of substituted phenylethylene can be α-methylstyrene, p-methylstyrene, o-ethyl styrene, ethylo benzene second Alkene, p -ethyl-styrene, p-tert-butylstyrene, 2,4- dimethyl styrenes etc..Aromatic ethylene base class compound can be preferred Ground is styrene.
Formed shell aromatic ethylene base class compound can be (C1-C10) alkyl methacrylate polymer or (C1-C10) polymer of alkyl acrylate.More specifically, (methyl) acrylate compounds can be polymethylacrylic acid Methyl esters (PMMA).
According to the second for the modified rubber that use (methyl) acrylate compounds of the illustrative embodiments of the disclosure are grafted The shell of alkenyl quasi-graft copolymer can be formed by copolymer of methyl methacrylatestyrene.
Herein, in shell, the amount based on copolymer of methyl methacrylatestyrene, methyl methacrylate It can be about 7 0wt% to about 83wt% and about 17wt% to about 30wt% with the respective amount of styrene.
The vinyl-based graft copolymer (B-2) of the modified rubber of use (methyl) acrylate compounds grafting of the disclosure Can be, such as Methyl Methacrylate-Butadiene-Styrene Copolymer (MBS).
Resin combination based on 100wt%, with the vinyl for the modified rubber that (methyl) acrylate compounds are grafted The amount of quasi-graft copolymer can be about 1wt% to about 15wt%, for example, about 2wt% to about 13wt% or about 3wt% are to about 10wt%.
The resin group of vinyl-based graft copolymer comprising the modified rubber being grafted with (methyl) acrylate compounds Improved impact resistance and heat resistance can be shown by closing object.
(B-3) aromatic ethenyl compound-ethenyl base cyanogen compound copolymer
Aromatic vinyl compound-vinyl cyanide compound copolymer passes through vinyl cyanide compound and aromatic vinyl The copolymerization for closing object is formed.
Vinyl cyanide compound can be selected from acrylonitrile, methacrylonitrile, flumaronitrile and combination thereof.
Aromatic vinyl compound, which can be selected from, can use halogen or C1 to the substituted or unsubstituted benzene second of C10 alkyl groups Alkene, α-methylstyrene and combinations thereof.
Vinyl cyanide compound-aromatic vinyl compound copolymer can be styrene-acrylonitrile copolymer (SAN).
Aromatic vinyl compound-vinyl cyanide compound copolymer resin can have about 60,000g/mol to about 350,000g/mol, for example, weight average molecular weight of about 70, the 000g/mol to about 180,000g/mol.
In resin combination according to illustrative embodiments, the resin combination based on 100wt% can be with about The amount of 1wt% to about 12wt%, particularly from about 2wt% to about 7wt% include aromatic vinyl compound-vinyl cyanide compound Copolymer resin.When including aromatic vinyl compound-vinyl cyanide compound copolymer except this range, with poly- carbonic acid The compatibility of ester resin may deteriorate, and therefore heat resistance may deteriorate.
(C) fluorinated polyolefin
In the exemplary embodiment, fluorinated polyolefin (C) can be such as polyflon, polyvinyl fluoride tree Fat, poly- fluoropropene resin, poly- fluorine butene resins, polyvinylidene fluoride, tetrafluoroethene/vinylidene fluoride copolymer, tetrafluoroethene/ Hexafluoropropylene copolymer and Tefzel.These can be independently operated, or can mix its different type.
Based on the total amount for the resin combination for showing good heat-resisting and insulation performance, the amount of fluorinated polyolefin (C) can Think about 0.01wt% to about 2wt%, more specifically about 0.1wt% to about 1.5wt%.When the amount of fluorinated polyolefin meets the model When enclosing, it can obtain with improved anti-flammability and the resin combination of impact resistance.
(D) fire retardant based on phosphorus
In the exemplary embodiment, the fire retardant based on phosphorus (D) can be represented for example by chemical formula 1.
[chemical formula 1]
Wherein, in chemical formula 1,
Each R6、R7、R9And R10It is independently C6 to C20 aryl groups or alkyl-substituted aryl group,
R8It is biphenyl phenolic group, and
N is 1 to 5 integer.
The alkyl substituent of alkyl-substituted aryl group can be C1 to C14 alkyl groups.
The fire retardant based on phosphorus that chemical formula 1 represents can be represented for example by chemical formula 1-1.
[chemical formula 1-1]
Wherein, in chemical formula 1-1, n is 1 to 4.
That is, can be such as biphenyl -4,4'- diyl tetraphenyl by the fire retardant based on phosphorus that chemical formula 1 represents Bis- (phosphates).
In addition, the fire retardant based on phosphorus represented by chemical formula 1 can exist as the mixture of oligomer.
According to embodiment of the present disclosure, in addition to the above compounds, the fire retardant based on phosphorus represented by chemical formula 1 Can be all compounds of the biphenyl phenols based on phosphorus, and this fire retardant can make as one or more compounds With.
Fire retardant (D) based on phosphorus can be with another phosphonium flame retardant, such as the mixing such as phosphate (ester), phosphonitrile.
Total amount based on resin combination, can be with about 1.5wt% to about 15wt%, and more specifically about 2wt% is to about The amount of 13wt% includes the fire retardant (D) based on phosphorus represented by chemical formula 1.It is represented when including in the range by chemical formula 1 The fire retardant based on phosphorus when, the resin combination according to illustrative embodiments for showing good heat-resisting and insulation performance Anti-flammability can be improved without deteriorating other performance.
(E) additive
Showing good heat-resisting and insulation performance resin combination can optionally further include according to its purposes Additive.Additive may further include antioxidant, releasing agent, lubricant, plasticizer, heat stabilizer, light stabilizer or Colorant, and can two or more additives be mixed according to the characteristic of end article.
Antioxidant can inhibit or block the chemical reaction of above-mentioned resin combination and oxygen, so as to prevent resin combination Decomposition and its intrinsic property loss, and including at least one in phenolic, phosphate type, thioether-type or amine type antioxidant Kind, but not limited to this.Antioxidant according to the present embodiment can include the first antioxidant and the second antioxidant.
Releasing agent improves the mouldability and stability of resin combination, and can be for example fluoropolymer, silicone oil, Stearic metal salt, the metal salt of montanic acid, montanic acid ester type waxes or polyethylene wax.
Lubricant lubricates the metal surface contacted with resin combination during extrusion method is moulded, so as to help to set The flowing or movement of oil/fat composition, and can be conventional use of material.
Plasticizer is used to increase the flexibility, process machinability or expansion character of resin combination, and can be conventional make Material.
The thermal decomposition of resin combination when heat stabilizer inhibits to mediate or mould at high temperature.
Light stabilizer can inhibit or prevent resin combination by ultraviolet light (UV) decompose and its color change therefore or Loss of mechanical properties, and can specifically include in hindered phenol type, diphenyl ketone type or benzotriazole type light stabilizer extremely Few one kind, but it is not limited to this.
Colorant can include general pigments or dyes.
The resin combination for showing good heat-resisting and insulation performance based on 100 parts by weight, can with about 0.01 to The amount of about 15 parts by weight includes additive.
It can be set according to good heat-resisting and insulation performance the resin combination that shows of the disclosure with well known prepare It is prepared by the method for oil/fat composition.For example, good heat-resisting and insulation performance resin combination is shown according to the disclosure It can be by the way that by component and other additives, mixing and melt kneading are fabricated to pellet in an extruder simultaneously.
Then, product in accordance with one embodiment of the present disclosure can have excellent heat-resisting and insulating properties by above-mentioned The resin combination of energy is formed.Show excellent heat-resisting and insulation performance resin combination show excellent anti-flammability, Insulating properties and heat resistance and excellent impact resistance and mobility.
According to the another exemplary of the disclosure, embodiment there is provided the products manufactured by resin combination.It can pass through Using resin combination, with various methods as known in the art, such as injection-molded, blowing, article of manufacture the methods of extrusion. Product can include the component of various Electrical and Electronic apparatus or ejecting product with complex shape, but not limited to this.
Product shows excellent insulation performance and anti-flammability.For example, product can have the CTI less than or equal to about 2 (relative discharge tracking index), and it is rated the range of V-0 in the test of UL94 Vertical Flames.
In another aspect, product can show excellent impact resistance and heat resistance.For example, according to ASTM D256, Product can be 1/8 " thickness under show about 60kgfcm/cm to about 90kgfcm/cm notched Chalpy impact it is strong Degree.In addition, about 25 to about 30 can be under conditions of 250 DEG C/10kg according to the melt flow index of ASTM D 1238 In the range of and under conditions of the about 220 DEG C/10kg in the range of about 10 to about 15.In addition, the dimension according to ASTM D1525 Card softening temperature may be in the range of about 110 DEG C to about 140 DEG C.
In this way, according to the resin combination for showing excellent heat-resisting and insulation performance of the disclosure and by its shape Into product show improved heat-resisting and insulation performance and excellent impact resistance and anti-flammability, therefore available for needing this Outside, component of various electrical/electronic apparatus of a little features etc..
Embodiment
Hereinafter, the disclosure is described in more detail with reference to embodiment and comparative example.However, provide for purposes of description with Lower embodiment and comparative example, and the disclosure is not limited to this.
The component that resin combination is used to prepare in embodiment and comparative example is as follows：
(A) polycarbonate resin
(A-1) bisphenol A polycarbonate resin has the weight average molecular weight (manufacturer of 28,000g/mol：Lotte Advanced Materials Co., Ltd.s, SC-1080)
(A-2) bisphenol A polycarbonate resin has the weight average molecular weight (manufacturer of 23,000g/mol：Lotte Advanced Materials Co., Ltd. SC-1190)
(B) vinyl-based copolymer
(B-1) styrene of g-ABS, wherein 55wt% and acrylonitrile (weight ratio：75/25) graft copolymerization is in 45wt%'s On the butadiene rubber of the equal grain sizes of Z with 310nm.
(B-2) the vinyl-based graft copolymer for the modified rubber being grafted with (methyl) acrylate compounds：Methyl-prop E pioic acid methyl ester-butadiene-styrene copolymer (MBS, manufacturer：Mitsubishi rayon, METABLEN C-223A)
(B-3) styrene of SAN resins, wherein 82wt% and the acrylonitrile polymerization (weight average molecular weight of 19wt%：130, 000g/mol)。
(C) fluorinated polyolefin
Polyflon (manufacturer：Pacific International, trade name：AD 001)
(anti-flammability)
(D) fire retardant based on phosphorus represented by chemical formula 1-1：
[chemical formula 1-1]
Wherein in chemical formula 1-1, n is 1 to 4 (manufacturer：Adeca corporation, trade name：FP900, biphenyl- 4,4'- diyl tetraphenyls are bis- (phosphate))
(1) fire retardant 1：Bisphenol-A bis (diphenyl phosphate) ester (manufacturer：Daihachi Chemical Industry Co., Ltd., trade name：CR741)
(2) fire retardant 2：Resorcinol diphenyl phosphate, (manufacturer：Daihachi Chemical Industry Co., Ltd., trade name：CR733S)
(3) fire retardant 3：Potassium diphenylsulfone sulfonate, (manufacturer：Arichem, trade name：KSS)
(4) fire retardant 4：Potassium perfluorobutane sulfonate (manufacturer：3M, trade name FR-2025)
Embodiment 1 to 4, comparative examples 1 to 5 and reference implementation example 1
Each resin combination according to embodiment 1 to 4, comparative examples 1 to 5 and reference implementation example 1 is prepared using these components Object is to be respectively provided with forming shown in table 1.According to manufacturing method, each component is mixed and there is composition as shown in Table 1, and Then squeezed out with 45 π double screw extruders and be fabricated to pellet.Herein, it squeezes out in 260 DEG C and RPM 250 times progress, and produces Pellet 80kg/ hours raw.By setting 120 tons of syringes under 260 DEG C of injection temperature and 60 DEG C of molding temperature, will make The pellet made is injection-molded into sample.
(table 1)
(unit：Wt%)
Assessment
The performance of sample manufactured in assessment embodiment 1 to 4 and comparative examples 1 to 5 and reference implementation example 1, as a result such as table 3 Shown in.
(1) cantilever beam impact strength (kgfcm/cm)：According to the appraisal procedure of ASTM D256, by assembling 1/8 " it is thick and The tool cantilever beam sample jaggy of 3.2mm long measures.
(2) melt flow index (MI)：According to the appraisal procedure of ASTM D 1238,250 DEG C/10kg or 220 DEG C/ It is measured under the conditions of each of 10kg.
(3) vicat softening temperature：According to ASTM D1525 and according to ISO 306/B50, in 5kgf and 50 DEG C/h of liter It is measured under the conditions of temperature.
(4) anti-flammability：According to UL-94 vertical checkouts, pass through ruler of the manufacture with 125 (w) × 12.5 (L) × 1.5 (H) mm Very little sample measurement.
(5) BPT (test of ball pressure)：According to KS C2006-1998, by the way that 3.0mm samples is made to pass through 125 DEG C, survey The numerical stability under the stress under high temperature is measured, and herein, excellent numerical stability is shown by the test.
Specifically, when being heated to 125 DEG C by the way that the steel ball with 5mm diameters is applied to the stationary load of 20 ± 4N Sample and when being formed with less than the dell of the diameter of 2mm, give " passing through ".
(6) CTI (relative discharge tracking index)：According to ASTM D3638-12, by measure the sample of 3.0mm not by The every 30 seconds NH that the concentration with 0.1wt% is added dropwise dropwise on sample surfaces4Voltage when Cl aqueous solutions reach 50 drops and are carbonized And it obtains.Reference table 2 is shown according to measurement voltage evaluation CTI in table 3.CTI is lower, obtains more excellent insulation characterisitic.
(table 2)
Tracking index range (voltage) The PLC specified
600≤TI 0
400≤TI ＜ 600 1
250≤TI ＜ 400 2
175≤TI ＜ 250 3
100≤TI ＜ 175 4
0≤TI ＜ 100 5
(table 3)
As shown in table 3, it is shown according to embodiment 1 to 4 comprising the resin combination of fire retardant represented by chemical formula 1 Excellent MI, and also show excellent heat resistance, impact strength, anti-flammability and insulation characterisitic.Especially, high resistant is obtained Combustion property and high insulating property.
On the contrary, the resin of bis-phenol, resorcinol and fire retardant based on metal organic sulfonate is included according to comparative examples 1 to 5 Composition but shows the anti-flammability deteriorated and impact resistance or the insulating properties of deterioration although excellent in flame retardance.
On the other hand, the resin combination of the xenol phosphorus type flame retardant except the scope of the present disclosure is included, that is, is referred to The resin combination of embodiment 1 but shows excellent anti-flammability and insulating properties, but show significantly reduced impact strength and Heat-resistant quality.
In other words, resin combination according to illustrative embodiments is together with polycarbonate resin, vinyl-based copolymer With fluorinated polyolefin together comprising the xenol phosphorus type flame retardant represented by chemical formula 1, it may thereby be ensured that excellent anti-flammability Excellent heat resistance and insulation performance are realized simultaneously with impact resistance.
The disclosure is described although having been combined and being presently believed to be practical example embodiment it should be appreciated that It is the present disclosure is not limited to disclosed embodiment, but on the contrary, it is intended to cover to be included in the spirit and model of appended claims Various modifications and equivalent arrangement design in enclosing.

Claims (12)

1. a kind of show good heat-resisting and insulation performance resin combination, comprising
(A) polycarbonate resin；
(B) vinyl-based copolymer；
(C) fluorinated polyolefin；With
(D) fire retardant based on phosphorus represented by chemical formula 1；
[chemical formula 1]
Wherein, in chemical formula 1,
Each R6、R7、R9And R10It is independently C6 to C20 aryl groups or alkyl-substituted aryl group,
R8It is biphenyl phenolic group, and the integer that n is 1 to 5.
2. according to claim 1 show good heat-resisting and insulation performance resin combination, wherein, it is described by changing The fire retardant (D) based on phosphorus that formula 1 represents is that biphenyl -4,4'- diyl tetraphenyls are bis- (phosphate).
3. according to claim 1 show good heat-resisting and insulation performance resin combination, wherein, based on described The total amount of good heat-resisting and insulation performance resin combination is shown, comprising
The polycarbonate resin of 65wt% to 94wt%；
The vinyl-based copolymer of 1wt% to 20wt%；
The fluorinated polyolefin of 0.01wt% to 2wt%；With
The fire retardant based on phosphorus represented described in 1.5wt% to 15wt% by chemical formula 1.
4. according to claim 1 show good heat-resisting and insulation performance resin combination, wherein, the poly- carbon It is equal with the weight different from first polycarbonate resin that acid ester resin includes (A-1) first polycarbonate resin and (A-2) Second polycarbonate resin of molecular weight.
5. according to claim 4 show good heat-resisting and insulation performance resin combination, wherein, described first The weight average molecular weight of polycarbonate resin in the range of 25,000g/mol to 32,000g/mol,
The weight average molecular weight of second polycarbonate resin is in the range of 20,000g/mol to 25,000g/mol.
6. according to claim 4 show good heat-resisting and insulation performance resin combination, wherein
The polycarbonate resin based on 100wt%, the polycarbonate resin include described the of 25wt% to 65wt% Second polycarbonate resin of one polycarbonate resin and 35wt% to 75wt%.
7. according to claim 1 show good heat-resisting and insulation performance resin combination, wherein, the ethylene Based co-polymers include
The vinyl-based graft copolymer of at least one (B-1) modified rubber,
(B-2) with (methyl) acrylate compounds be grafted modified rubber vinyl-based graft copolymer and
(B-3) aromatic vinyl compound-vinyl cyanide compound copolymer.
8. according to claim 7 show good heat-resisting and insulation performance resin combination, wherein, the rubber Modified vinyl-based graft copolymer is acrylonitrile-butadiene-phenylethene grafted copolymer g-ABS.
9. according to claim 7 show good heat-resisting and insulation performance resin combination, wherein, with (methyl) The vinyl-based graft copolymer of the modified rubber of acrylate compounds grafting is methyl methacrylate-butadiene-benzene second Alkene copolymer MBS.
10. according to claim 7 show good heat-resisting and insulation performance resin combination, wherein, aromatics second Alkenyl compound-vinyl cyanide compound copolymer is styrene-acrylonitrile copolymer SAN.
11. a kind of product manufactured by resin combination described in claim 1.
12. product according to claim 11, wherein, the product has 0 to 2 measured according to ASTM D3638-12 Relative discharge tracking index CTI.
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Application publication date: 20180710